Aliphatic amido propyl quaternary ammonium salts



Patented Mar. 18, 1952 rss PATENT osrics ALIPHATIC ABHDO PROPYLQUATERNARY AMLIHONIUM SALTS ration of Maine No Drawing. Application May24, 1947, Serial No. 750,366

Claims. (Cl. 260-4045) The present invention relates to the productionof new organic ammonium compounds, and relates more particularly toquaternary ammonium compounds which are suitable for various uses suchas wetting agents, detergents, emulsifying agents, germicides,fungicides and the like.

The compounds of the invention are defined by the general formulawherein R is a member of the group consisting of aliphatic and alicyclicradicals containing at least 7 carbon'atoms such as nonyl, undecyl,tridecyl, heptadecyl, the residue of abietic acid, and the likeradicals; R1 and R2 are members of the group consisting of alkyl andhydroxyalkyl radicals of l 3 carbon atoms such as, for example, methyl,ethyl, propyl, isopropyl, hydroxyethyl, dihydroxypropyl, and the likeradicals; R3 is a hydroxyalkyl radical of 1-3 carbon atoms such as, forexample, hydroxyethyl, hydroxypropyl, dihydroxypropyl and the like; andY is an anion such as, for example, halogen, hydrogen sulfate,thiocyanate, etc.

The new compounds are for the most part thick liquids or amorphoussolids having no definite melting points and which are readily solublein water and form stable aqueous solutions. The compounds are alsoreadily soluble in the ordinary organic solvents such as ethanol,acetone, ether, toluene, and the like. Because of their excellentdispersing properties, they exert a remarkable action as wetting andemulsifying agents, and also have been found to be particularly suitablefor rewetting uses and as assistants in stripping vat dyes fromcellulosic textile materials.

As noted above, R may be any aliphatic or alicyclic radical containing asufiicient number of carbon atoms to provide a hydrophobic radical whichwill produce orientation of the compounds at an oil-water interface. Itis an advantage of the invention that a wide variety of monocarboxylicacids may be used for this purpose such, for example, as caproic acid,decenoic acid, lauric acid, myristic acid, palmitic acid, stearic acid,

arachidic acid, oleic acid and other more highlyunsaturated fatty acidsof 14-18 carbon atoms obtained from vegetable and animal oil and-fatssuch as soya bean oil, cottonseed oil, coconut oil, linseed oil, castoroil, dehydrated castor oil and the like, or from other commercialsources such as tall-oil. Alicyclic monocarboxylic acids which may beused include petroleum naphthenic acids of 7-14 carbon atoms havingboiling points within the range of 2l5-310 C., as described in Ellis,Chemistry of Petroleum Derivatives," (1934) edition) pagesl062-1085,,abietic acid, and the like.

It will be apparent that the number of carbon atoms contained by thealiphatic or alicyclic radicals is largely dependent on the purpose towhich the quaternarized compound is to be put. Thus, for some purposesit may be desirable that B. may contain in excess of 20 carbon atomsalthough for most wetting, emulsifying, and the like uses we have foundthat it is more desirable that R shall contain not more than about 20carbon atoms and, preferably, for the most ready dispersibility inaqueous media, shall not contain more than 19 carbon atoms.

Representative compounds which fall within the scope of this inventionare:

I cmcmon 0111,50 ONHfHzh-N-CH;

Caprylamidopropyldimethyl-beta'-hydroxyethyl ammonium chlorideGamma-stearamldopropyl-dlmethyl-dihydroxypropyl ammo nium chloride01.11350 oNH cn,)=-N. cmon,oma

Gamma-stearamidopropyl-tris (beta-hydroxyethyl) ammo nium chloridecrncniou I Lauramidopropylmethyl-bis (beta-hydroxyethyl) ammoniumchloride C HiC H: O H C mHnC 0 NH (CH1) r-MGH;

1 CH; 7 Abletamidopropyldimethyl-beta-hydroxyethyl ammonium chloride Thepresent invention is a continuation-in-par of application Serial Number521,588 of Elmer W Cook and Philip H. Moss, filed February 8, 1944 nowPatent No. 2,459,062, issued January 11, 1949 The preferred method ofpreparing the nove quaternary ammonium salts of this, inventior isdescribed in that application and mar be ex assassiressed by thefollowing equations and descripion:

CHg=CH-CN where R1 and R2 are as defined above.

The invention is further illustrated by the ollowing examples:

Example 1 To 126 gm. (2.4 mols) of acrylonitrile was .dded slowly 250gm. (2.4 mols) of diethanol unine. After the addition was completed andhe exothermic reaction had ceased, the soluion was heated for 2.4 hourson a steam bath. liter vacuum stripping of the product at 100 C.. #56gm. of beta-di-(hydroxyethyl) aminopro iionitrile was obtained.

350 gm. of this aminonitrile was hydrogenated Lt 2000 p. s. i. at 115 C.in the presence of about ,0 gm. of Raney nickel and 4.4 mols ofanhydrous immonia. The product was vacuum distilled, 'ielding 275 gm.(76%) of gamma-di-(betaiydroxyethyl) aminopropylarnine, having a boilngpoint of l75-187 C. at 8.6 mm.

56.8 gm. stearic acid and 33 gm. of the above lescribed aminopropylaminewas dissolved in tbout 50 gm. of toluene. was carried out under refluxconditions at 155- .61" C. for a period of 9 hours. Thereafter theoluene and water of reaction was removed by acuum distillation leaving88 gm. of gamna-stearamidopropyl di (beta'-hydroxyethy1) mine, a tan,brittle solid at room temperature.

105 gm. (0.245 mol) oi. the above described tmidopropylamine wasdissolved in 225 cc. of ethanol. To this solution was added 22.4 cc. of:oncentrated hydrochloric acid. The solution was heated to 62 0., and 16gm. ethylene oxide vas passed into the heated solution. After a 'eactionperiod of four hours at'70 C. the solvent vas removed by distillation.The product was stifi, dark. and partially opaque at 100 C., and yes ahard opaque solid at room temperature. [*he quaternary ammonium salt wascompletely :oluble in warm water and the ordinary organic :olvents. Thiscompound was found to possess iarticularly desirable characteristics asan assist- Lnt for stripping vat dyes from cellulosic textile naterialsand also as a rewetting agent.

The acylation reaction Erample 2 Into 545 gm. of a 25% aqueous solutionof dimethyl amine, cooled with ice and water, there were added from adropping funnel 170 gm. oi acrylonitrile. was controlled so that thetemperature in the reaction vessel remained below 20 C. After the coldreaction mixture had stood for one hour, it was poured into 350 cc. of10% aqueous sodium hydroxide solution, the oily layer collected and theaqueous layer extracted with ether. The extract and the oily layer weredried over sodium sulfate and distilled. 218 gm. ofbeta-dimethylaminopropionitrile were collected at 73"- 74" C./22 mm.

207 gm. of beta-dimethylaminopropionitrile were hydrogenated in anautoclave under a pressure of about atmospheres at C. in the presence of72.4 gm. of anhydrous ammonia, using Raney nickel as the catalyst. Theproduct was dried over solid potassium hydroxide and vacuum distilled.204.5 gm. of gamma-dimethylaminopropylamine were collected, B. P. 134 C.at atmospheric pressure.

38 gm. of myristyl chloride were added dropwise to a solution of 15.5gm. of gamma-dimethylaminopropylamine in 160 gm. of benzene. After onehour of stirring, the benzene solution was washed with 10% aqueoussodium hydroxide. The benzene layer was then washed once with water andthe solvent removed by vacuum distillation. The residue was distilled at208- 215 C./1-2 mm., giving a solid distillate ofgamma-myristamidopropyldimethylamine.

266 gm. (0.852 mol) of gamma-myristamidopropyldimethylamine wasdissolved in 450 gm. of ethyl alcohol to which was added 90.5 cc. (1.1mol) of concentrated hydrochloric acid. 40 gm. (0.9) mol) of ethyleneoxide were passed into the solution and the reaction was continued at atemperature of 80 C. for 3 hours. The solvent was then removed bydistillation under reduced pressure. The product wasgammamyristamidopropyldimethyl beta-hydroxyethyl ammonium chloride, alight .brown amorphous solid, soluble in warm water, alcohol, toluene,ether, etc.

Example 3 250 gm. methylamine, prepared in a manner similar to that ofpreparing the amidoamine of Example 1.

Example 4 7.4 gm. (0.02 mol) of beta'-myristamidoethyldimethylamine wasdissolved in ethanol" in a flask equipped with an air condenser. Thesolution was heated with 2 gm. (0.025 mol) of ethylene chlorhydrin at atemperature of -140 C. for 3 hours. The product, beta-myristamidoethyldimethyl beta hydroxyethylammonium chloride was a soft, watersoluble solid at room temperature.

The rate of addition of the nitrile (1.1 mol) of caprylamidopropyldiasaasrs Example 5 221 gm. (0.73 mol) of wood rosin acid and 100 gm.(0.98 mol) of gamma-dimethylaminopropylamine was heated over a metalbath at a temperature of 200-215 C. and the water of reaction wasremoved with a benzene carrier.

93 gm. (0.24 mol) of the so-produced gammaabietamidopropyldimethylaminewas dissolved in an equal weight of alcohol and to this solution wasadded 20 cc. (0.24 mol) of hydrochloric acid. About 12 gm. (0.27 mol) ofethylene oxide was passed into the solution. The mixture was allowed tostand overnight at a temperature of about 46 C. The product,gamma-abietamidopropyldimethyl beta-hydroxyethyl ammonium chloride, wasa tan solid, soluble in alcohol, acetone, ether, and quite soluble inwarm water.

Example 6 206 gm. of gamma-stearamidopropyldimethylamine was dissolvedin 300 gm. of ethanol. To this solution was added a slight excess ofconcentrated hydrochloric acid, such that the final pH of the solutionwas 3.9. The solution was heated to 40-45 C. and an equivalent weight ofethylene oxide was passed into it. The reaction product,gamma-stearamidopropyldimethylhydroxyethylammonium chloride, was a tansolid which was readily soluble in water.

Example 7 468 gm. of gamma-lauramidopropyldimethylamine and 133 gm. ofethylene chlorhydrin was heated at 125 C. for 2 hours, the reactionmixture being stirred during the mild exothermic reaction. The productgamma-lauramidopropyldimethylhydroxyethylammonlum chloride. was a brown,opaque, brittle solid which was readily soluble in water.

Example 8 .A mixture of 117 gm. of gamma-stearamidopropyldimethylamineand 35 gm. of alpha-glycerolchlorhydrin was stirred and heated at 125 C.for 1.5 hours. The quaternary ammonium salt, gammastearamidopropyldimethyl beta',gam-

d ma'-dihydroxypropyl ammonium chloride, was a tan opaque solid whichwas water soluble in fairly high concentrations.

What we claim is:

1. A quaternary ammonium compound having the general formula wherein Ris a member of the group consisting of aliphatic and alicyclic radicalscontaining at least 7 carbon atoms, R1 and R2 are members of the groupconsisting of alkyl and hydroxyalkyl radicals of 1-3 carbon atoms, R: isa hydroxy in claim 1 in which Y is ELMER W. COOK. PHILIP H. MOSS.

REFERENCES CHE!) The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Number Name Date 1,737,458 Hartmann et al. Nov.26, 1929 1,860,563 Wayne May 31, 1932 2,085,706 Schoeller June 29, 19372,329,406 Mauersberger Sept. '14, 1943 2,345,570 Bley Apr. 4, 19442,362,760 Maxwell Nov. 14, 19% 2,459,062 Cook et al Jan. 11, 1949 OTHERREFERENCES Organic Chemistry by Karrer, 1946 ed., page 122.

1. A QUATERNARY AMMONIUM COMPOUND HAVING THE GENERAL FORMULA